Search

In recent years, incidents of pesticide pollution and abuse of feed additives have occurred frequently, which pose a great threat to human health. Raman spectroscopy has become an important method in the field of food safety due to its rapidity, simplicity and sensitivity. It is important to obtain complex structure to promote surface-enhanced Raman scattering (SERS) effect. In this study, gold helical nanoparticles with rich surface structure were synthesized using cysteine as induce agent. Notably, the complex helical structure and tip led to an excellent electromagnetic enhancement property. The helical structure showed ultra-sensitive detection of hazardous molecular, such as thiram and ractopamine. Interestingly, the D/L-Au structure had significant chiral optical activity and could be used as an unlabeled SERS platform for enantiomer identification. This study provided an effective strategy for the detection of pesticides and feed additives, which could be applied in other aspects of food safety in the future. [Display omitted] • A convenient strategy for preparing Raman substrates was provided. • The gold helix was an excellent Raman substrate. • It could analyze harmful chemical residues in food. • It could recognize amino acid enantiomers and expanded the application range of SERS. [ABSTRACT FROM AUTHOR]

In this work, a density functional theory (DFT) study was performed to identify the catalytically active species in the copper-catalyzed three-component reductive hydroxymethylation of styrene with CO 2 and hydrosilane. The calculations reveal that the dimeric copper(I) hydride species, formed in a mixture of the bisphosphine ligand, Cu(OAc) 2 , and hydrosilane, probably acts as the catalyst precursor. In the beginning, this species is catalytically competent to trigger the hydrocupration of styrene, along with the formation of the dimeric copper(I) alkyl intermediate. Subsequently, CO 2 insertion into the dimeric copper(I) alkyl intermediate occurs, which is accompanied by the cleavage of the Cu-Cu bond and the generation of the monomeric copper(I) carboxylate intermediate. In the end, the sequential reduction of the monomeric copper(I) carboxylate intermediate with the hydrosilane produces the monomeric copper(I) hydride species as the actual catalyst and turns on the catalytic cycle. On the other hand, the monomeric copper(II) hydride species, yielded as the kinetic product in the initial reaction of the bisphosphine ligand, Cu(OAc) 2 , and hydrosilane, is also reactive for the hydrocupration of styrene. However, the resulting monomeric copper(II) alkyl intermediate is found to be the catalyst resting state, because of the much higher energy barrier demanded for the subsequent nucleophilic attack toward CO 2 . On the basis of the results of an activation-strain model (ASM) analysis and charge decomposition analysis (CDA), the low activity of the monomeric copper(II) alkyl intermediate can be ascribed to the more crowded environment around the central copper(II) ion and the weaker nucleophilicity of the alkyl moiety. Furthermore, all of the possible CuH species generated in the system are competent to promote the two-component hydrosilylation of CO 2 with hydrosilane, which is an inevitable side reaction along with the reductive hydroxymethylation of styrene with CO 2 and hydrosilane.